The present invention relates to new nitrogeneous multiacrylic monomers, a process for their preparation and their application to the synthesis of new polymers.
Through the patent publication WO 86/06716 are already known monomers having the formula: ##STR1## wherein R.sub.1 is an acrylic or methacrylic group corresponding to the formula ##STR2## R.sub.3 being selected from a hydrogen atom and a methyl group, R.sub.2 is a hydrogen atom, a saturated aliphatic group comprising up to 10 carbon atoms or a group identical to R.sub.1 ; and
R is a bivalent group comprising at least one substituted or non-substituted aliphatic or aromatic ring. PA1 R.sub.1, R.sub.2, R.sub.3, R.sub.5, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are selected, independently from each other, from a hydrogen atom and acrylic or methacrylic groups having the formula ##STR4## R.sub.10 being selected from a hydrogen atom and a methyl group, X being selected from the sulfur and oxygen atoms and R' being a hydrocarbon group of 2 to 20 carbon atoms comprising a hydroxyl group within the backbone or at the end of the chain, selected from linear or branched alkyl groups, monocyclic or polycyclic cycloalkyl or heterocycloalkyl groups and alkylaryl groups, PA1 R.sub.4 is a group having the formula --CH.sub.2 --O--R.sub.11 --O--CH.sub.2 -- wherein R.sub.11 is a bivalent group selected from alkylene groups having from 2 to 12 carbon atoms and those comprising at least a substituted or non-substituted aliphatic or aromatic ring, and PA1 R is a bivalent group comprising at least one substituted or non-substituted aliphatic or aromatic ring, PA1 when n is 0, at least 2 of the groups R.sub.1, R.sub.2, R.sub.3, R.sub.7, R.sub.8 and R.sub.9 are acrylic or methacrylic groups, and PA1 when n is higher than 0, at least 2 of the groups R.sub.1, R.sub.2, R.sub.3, R.sub.5, R.sub.6, R.sub.7 R.sub.8 and R.sub.9 are acrylic or methacrylic groups. PA1 an unsaturated nitrile such as acrylonitrile or methacrylonitrile, PA1 a N-substituted maleimide such as N-ethylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-tertiobutylmaleimide, N-n-octylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and N-phenylmaleimide, PA1 acrylic and methacrylic oxazolidones selected from those of formulae: ##STR9## wherein R.sub.1 is selected from a hydrogen atom and a methyl group, PA1 n is an integer from 1 to 12, PA1 m is an integer from 1 to 3, and PA1 R.sub.2 is a linear or branched alkyl or cycloalkyl or aromatic hydrocarbon radical having from 5 to 12 carbon atoms, PA1 a vinylaromatic hydrocarbon such as styrene, vinyltoluene, alphamethylstyrene, chlorostyrenes, betamethylstyrene, p-tertiobutylstyrene or vinylnaphtalene, PA1 an alkyl ester of acrylic or methacrylic acid, PA1 a monocyclic (such as those of cyclohexyl or benzyl) or bicyclic (such as those of isobornyl) acrylate or methacrylate, PA1 diallyl phtalate, or PA1 a polyol acrylate or methacrylate such as the diacrylates and dimethacrylates of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-ethyl-1,3propanediol, 2,2-diethyl-1,3 propanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, trimethylolethane, trimethylolpropane, glycerol and pentaerythritol, the triacrylates and trimethacrylates of trimethylolethane, trimethylolpropane, glycerol and pentaerythritol, the tetraacrylates and tetramethacrylates of pentaerythritol, the di(meth)acrylates up to hexa(meth)acrylates of dipentaerythritol, poly(meth)acrylates of mono- or polyethoxylated or mono- or polypropoxylated polyols such as triacrylate and trimethacrylate of triethoxylated trimethylolpropane, tripropoxylated trimethylolpropane and tripropoxylated glycerol, triacrylate, trimethacrylate, tetraacrylate and tetramethacrylate of tetraethoxylated pentaerythritol and caprolactone methacrylate.
These monomers lead, by radical polymerisation or copolymerisation, to polymers having thermal properties significantly better than those obtained from conventional acrylic monomers. However the applicant discovered that these polymers have the disadvantage of an important brittleness probably due to their too high crosslinking density. On the other hand, the synthesis of the monomers (A) involves a glycidyl acrylate or methacrylate whose reactivity with a diamine having the formula H.sub.2 N--R--NH.sub.2 is insufficient under the conditions described in this document.